DE598678C - Process for the production of Kuepen dyes - Google Patents

Description

Process for the production of vat dyes It has been found that vat dyes that contain an indigo, and an anthraquinoid radical, can be produced if you have a carboxyl group or a reactive one in the naphthalene nucleus Derivative of such a group substituted naphthioindoxyls or their reactive ones a- or ß-derivatives in any order with for the production of indigoid Components suitable for dyes and with aminoanthraquinones or their substitution products condensed.

It has also been found that those .der after .this method manufacturable new vat dyes, which must be addressed as symmetrical, can also be obtained if one is on the naphthalene nucleus by a carboxyl group or a reactive derivative of such a group substituted naphththioindoxyls or their 2-carboxylic acids oxidizing agents and aminoanthraquinones in any order or allows their substitution products to act. The new dyes can do both can be used for dyeing as well as in printing; they result in the most diverse Shades of very good fastness properties. These are in many cases through Treatment of the dyes with halogens or halogen-releasing agents is still improved.

The new dyes can be converted into leuco ester salts by known methods be transferred. Example r 24, q.Parts 2, x-naphththioindoxyl-5-carboxylic acid dissolved in dilute soda; air is passed through this solution until the Formation of the 2, 1,: 2 ', r'-naphthioindigo-5, 5'-dicarboxylic acid is complete. These is precipitated by acidification, filtered and dried. She puts a brown one Powder that dissolves in sulfuric acid with a yellow color.

24.2 parts of this fan material are heated with 30 parts of thionyl chloride and zoo parts of o-dichlorobenzene until the formation of the 2, i, 2 ', i'-naphthioindigo-5, 5'-dicarboxylic acid chloride has ended. This is filtered, washed with o-dichlorobenzene and then heated to 180 ° with a suspension of 68 parts of i-aminoq-benzoylaminoanthraquinone in 250 parts of nitrobenzene. It is then cooled 1 °, filtered and dried. The new dye in the formula is a red-brown powder that dissolves in sulfuric acid with a purple color. It dyes cotton from a red-brown vat in red-brown shades with good fastness properties.

The 2, i-naphththioindoxyl-5-carboxylic acid used as the starting product can e.g. B. be prepared in the following way: i-amino-6-naphthalenesulfonic acid is converted into i-cyano-6-naphthalenesulfonic acid by diazotizing and treating with K.upfercyanür transferred, from .the i-cyano-6-naphthalene sulfochloride by the action of phosphorus pentachloride is obtained. This is treated with zinc and sulfuric acid until not only the reduction of the sulfochloride group, but also the saponification of the cyano group is completed. The 2-merleapto-5-naphthoic acid thus obtained becomes more alkaline Solution condensed with chloroacetic acid, whereby the 5-carboxy-2-naphthylthioglycol, acid arises. This crystallizes from chlorobenzene in colorless needles with a melting point 2i6 °. The 5-carboxy-2-naphthylthioglycolic acid is then mixed in with o-dichlorohenzene Phosphorus trichloride is heated until the corresponding dicarboxylic acid chloride is formed; then aluminum chloride is added and the mixture is stirred for a longer time at about 5 to 3s °. In the steam distillation that follows to remove the o-dichlorobenzene .des The reaction mixture discharged in water becomes that in the 5-position C O Cl group saponified to the carboxyl group, and the 2, i-I "Taphtli thioindoxyl-5-carboxylic acid is obtained, which can be purified by dissolving from soda and reprecipitating from acetic acid. she forms a pale yellow colored powder that does not yet melt at 24o °. example e 2q., 5 parts of 2, i-naphthtrioindoxyl-5-carboxylic acid and 33 parts of 2- (p-dimethylamino) anil of the q.-methyl-6-chloro-3-oxythionaphthens are heated in zooo parts of alcohol, until the condensation to the indigoi.den dye has ended. It is then filtered and dried. The new dye is a crimson powder that is Dissolves in sulfuric acid with a green color.

38 parts of this dye are heated with 26 parts of thionyl chloride in zoo parts of o-dichlorobenzene until the formation of the carboxylic acid chloride has ended. This is filtered; washed with a little o-dichlorobenzene and then heated to 180 ° with a suspension of 29 parts of i-amino-q.-benzoylaminoanthraquinone in 250 parts of nitrobenzene. It is allowed to cool and filtered. The new dye in the formula forms a burgundy red @ u.lver that dissolves in sulfuric acid with an olive green color. It dyes cotton from a red-brown vat in brown-red shades with very good fastness properties. EXAMPLE 3 If the 2- (p-dimethylamino) -anil of 4-methyl-6-chloro-3-oxythionaphthens is replaced by the 2- (p-dimethylamine) -anil of 2, i-naphthioindoxyl in the examples the 5-carboxylic acid of 2, 1, 2 ', i'-naphththioindigo. This is a brown dye that dissolves in sulfuric acid with a blue color. If the carboxylic acid chloride is prepared from this body analogously to the information in Example 2 and this is condensed with i-amino-4-benzoylaminoanthraquinone, a dye of the formula is obtained This is a brown powder that dissolves in sulfuric acid with a blue color. It dyes cotton from a brown vat in red-brown shades with excellent fastness properties. Example 4 2 [, 5 parts of 2, i-naphththioindoxyl- [carboxylic acid and 33 parts of 2- (p-dimethylamino) anil des 2, i-naphththioindoxyls are heated in 2ooo parts of alcohol until the condensation to indigoid Dye is finished. It was then filtered and dried. The new dye is a dark brown powder that dissolves in sulfuric acid with a blue color.

44 parts of this dye are heated with 15 parts of thionyl chloride in zoo parts of o-dichlorobenzene until the formation of the carboxylic acid chloride has ended. This is filtered, washed with a little o-dichlorobenzene and then heated to -75 ° with a suspension of 34 parts of i-amino-5-benzoylaminoanthraquinone in 250 parts of nitrobenzene. It is allowed to cool and filtered. The new dye in the formula forms a dark brown powder that dissolves in sulfuric acid with a blue color. It dyes cotton from a red vat in yellowish brown shades with very good fastness properties.

Will the 2, 1,: 2 ', i'-naphththioindgocarboxylic acid instead of i-amino-5-benzoylaminoanthraquinone condensed with 22 parts of a-aminoanthraquinone, the result is a brown dye, the cotton from the reddish brown vat also dyes in yellowish brown tones.

The condensations of 2, 1, 2 ', i'-naphthioindigo-4-carboxylic acid with i-amino-4 = benzoylaminoanthraquinone or with i-amino-4-methoxyanthraquinone also give brown dyes, cotton in pure brown shades with very good fastness properties stain. Example In Example 4, the 2, i-napliththioindoxyl-4-carboxylic acid is replaced by the 2, i-naphththioindoxyl-3-carboxylic acid and condensation in the procedure given there with components suitable for the preparation of indigoid dyes and with aminoanthraquinones or theirs Substitution products, mixed vat dyes of various shades are obtained, as can be seen from the table below. Indigoid component Anthraquinone component Color of the color Color Color of the dye in Hü SO, the vat Coloring 2- (p-dimethylamino) -anil i-amino-5-benzoylamino- green- brown violet- olive green of the 2, 3 - naphththioin anthraquinone black brown -doxyls 2- (p-dimethylamino) -anil i-amino-4-benzoylamino- violet- brown violet- heliotrope des 2; 3-naphththioin anthraquinone black brown doxyls 2- (p-dimethylamino) anil i-amino-5-benzoylamino dark heliotrope brown yellow-brown the 2, i-naphththioin anthraquinone brown doxyl-3-carboxylic acid.

Acenaphthenchinon i-Amino-q.-benzoylamino- brown olive brown brick red anthraquinone acenaphthenquinone i-amino-5-benzoylamino- brown brown brown orange anthraquinone 2- (p-dimethylamino) -anil i-amino-5-benzoylamino- brown green olive reddish ¢ -Methyl-6-chloro-anthraquinone brown brown 3-oxythionaphthens 2- (p-dimethylamino) anil i-Amino-4-benzoylamino- red-brown green olive- Bordeaux des 4-methyl-6-chloro-anthraquinone Brown. 3-oxythionaphthens 2- (p-dimethylamino) -anil i-amino-5-benzoylamino brown heliotrope olive-yellow-brown of 6-ethoxy-3-oxythio-anthraquinone brown naphthene 2- (p-dimethylamino) -anil i-Amino-q.-benzoylamino- brown heliotrope olive- Bordeaux des 6-ethoxy-3-oxythio- anthraquinone brown naphthens 2- (p-dimethylamino) -anil i -amino - q. - methoxyan- brown violet olive yellowish 6-ethoxy-3-oxythiothrachinone brown Bordeaux naphthens 2- (p-dimethylamino ', - anil i-amino-5-benzoylamino- black- blue brown yellow-brown des 2, i-naphththioin-anthraquinone brown doxyls 2- (p-dimethylaniino) -anil i-Amino-q.-benzoylamino- black- blue brown reddish 2, i-naphththioin-anthraquinone brown brown doxyls

Claims (1)

PATENT CLAIMS: i. Process for the production of vat dyes, the one. indi.goiden and an anthraquinone contain the remainder, characterized by, that one in the naphthalene nucleus by a carboxyl group or a reactive derivative such (group of substituted naphthioindoxyls or their reactive a- or ß-derivatives in any order with for the production of indigoid Components suitable for dyes and with aminoanthraquinones or their substitution products condensed. a. Process for the production of vat dyes which have an indigo-den and contain an anthraquinoid radical, characterized in that im Naphthalene nuclei through a carboxyl group or a reactive derivative of a such group substituted naphthioindoxyls or their 2-carboxylic acids in any Order of oxidizing agents and aminoanthraquinones or their substitution products can act and optionally halogenated the products obtained.